9-isopropylidene-9H-fluorene | 19326-47-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: 9-isopropylidene-9H-fluorene
• 英文别名: 9-isopropylidenefluorene；9-Isopropyli-denefluorene；9-propan-2-ylidenefluorene
• CAS: 19326-47-7
• 化学式: C₁₆H₁₄
• 分子量: 206.287
• InChiKey: MOYQKHHWZVQHCY-UHFFFAOYSA-N

物化性质

• 熔点：
  113-117 °C
• 沸点：
  332.6±12.0 °C(Predicted)
• 密度：
  1.084±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  16
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  9-isopropylidene-9H-fluorene 在 potassium sulfate 、 potassium hydrogensulfate 、 oxone 、 丙酮 作用下， 以 水 为溶剂， 反应 24.0h， 以92%的产率得到9-oxy-9-(α-oxy-isopropyl)-fluorene
  参考文献：
  名称：

  Reaktivit�t und Selektivit�t bei der Oxidation von Styrolderivaten. IV. Untersuchungen zur Oxidation von substituierten ?,?-Dimethylstyrolen

  摘要：

  The liquid phase oxidation of substituted (p-MeO-, p-Cl-, m-CF3-) 2-aryl-3-methyl-but-2-enes, of 1,1-diphenyl-2-methyl-propene, of 1-ethoxy-2-methyl-1-phenyl-propene and of 9-isopropylidene-fluorene with pure oxygen was investigated in chlorobenzene solution and in presence of cumene and of cumene hydroperoxide in the temperature range 65-125 degrees C. The product yields were determined gaschromatographically. The differences of the activation energies of epoxide formation and the parallel reactions were calculated. They amount to 19-48 kJ/mol. The epoxide selectivity increases with increasing temperature and increasing concentration of olefin. The relative chain propagation constants (k(pC=C)) were determined by competitive oxidation with cumene. The k(pC=C) values of substituted beta,beta-dimethylstyrenes can be correlated by a LFE-relationship with the ionisation energies of the olefins.

  DOI：

  10.1002/prac.19983400308
• 作为产物：
  描述：

  9-oxy-9-isopropyl-fluorene 在 对甲苯磺酸 作用下， 以 甲苯 为溶剂， 以88%的产率得到9-isopropylidene-9H-fluorene
  参考文献：
  名称：

  Reaktivit�t und Selektivit�t bei der Oxidation von Styrolderivaten. IV. Untersuchungen zur Oxidation von substituierten ?,?-Dimethylstyrolen

  摘要：

  The liquid phase oxidation of substituted (p-MeO-, p-Cl-, m-CF3-) 2-aryl-3-methyl-but-2-enes, of 1,1-diphenyl-2-methyl-propene, of 1-ethoxy-2-methyl-1-phenyl-propene and of 9-isopropylidene-fluorene with pure oxygen was investigated in chlorobenzene solution and in presence of cumene and of cumene hydroperoxide in the temperature range 65-125 degrees C. The product yields were determined gaschromatographically. The differences of the activation energies of epoxide formation and the parallel reactions were calculated. They amount to 19-48 kJ/mol. The epoxide selectivity increases with increasing temperature and increasing concentration of olefin. The relative chain propagation constants (k(pC=C)) were determined by competitive oxidation with cumene. The k(pC=C) values of substituted beta,beta-dimethylstyrenes can be correlated by a LFE-relationship with the ionisation energies of the olefins.

  DOI：

  10.1002/prac.19983400308

文献信息

• Hydrogenation reactions with hydridocobalt Tetracarbonyl
  作者：Theodore E. Nalesnik、John H. Freudenberger、Milton Orchin

  DOI：10.1016/s0022-328x(00)89054-3

  日期：1981.12

  The tetrasubstituted ethylene, bifluorenylidene, reacts very rapidly (4.06 X 10−2 1 mol−1 sec−1 at 0°C) with HCo(CO)4 to give bifluorenyl. α-Phenylacrylonitrile (atroponitrile) reacts even more rapidly under the same conditions (6.0 l mol−sec−1). Other highly substituted ethylenes react very slowly with HCo(CO)4, indicating considerable steric effects. The data are consistent with radical type intermediates

  四取代的乙烯，联芴基，与HCo（CO）4非常迅速地反应（0°C时为4.06 X 10 -2 1 mol -1 sec -1），得到联芴基。在相同的条件下（6.0 l mol - sec -1），α-苯基丙烯腈（a腈）的反应甚至更快。其他高度取代的乙烯与HCo（CO）4的反应非常缓慢，表明存在很大的空间效应。数据与自由基型中间体一致。
• α-Bromoacrylic Acids as C1 Insertion Units for Palladium-Catalyzed Decarboxylative Synthesis of Diverse Dibenzofulvenes
  作者：Minghao Zhang、Wenbo Deng、Mingjie Sun、Liwei Zhou、Guobo Deng、Yun Liang、Yuan Yang

  DOI：10.1021/acs.orglett.1c01888

  日期：2021.8.6

  Herein α-bromoacrylic acids have been employed as C1 insertion units to achieve the palladium-catalyzed [4 + 1] annulation of 2-iodobiphenyls, which provides an efficient platform for the construction of diverse dibenzofulvenes. This protocol enables the formation of double C(aryl)–C(vinyl) bonds via a C(vinyl)–Br bond cleavage and decarboxylation. It is particularly noteworthy that the method features

  在本文中，α-溴丙烯酸已被用作 C1 插入单元以实现钯催化的 2-碘联苯的 [4+1] 环化，这为构建各种二苯并富烯提供了一个有效的平台。该协议能够通过 C(乙烯基)-Br 键裂解和脱羧形成双 C(芳基)-C(乙烯基)键。特别值得注意的是，该方法具有广泛的底物范围，并且可以成功地将各种有趣的框架，如桥环、稠（杂）芳环和二乙烯基苯结合到产品中。
• Synthesis, Structural Characterization, Ligand Displacement Reaction, and Electrochemical Property of Ruthenium Complexes Incorporating Linked Cyclopentadienyl-Carboranyl Ligands
  作者：Yi Sun、Hoi-Shan Chan、Pierre H. Dixneuf、Zuowei Xie

  DOI：10.1021/om0493816

  日期：2004.11.1

  1,2-bis(diphenylphosphino)ethane), [η5:σ-Me2C(C5H4)(C2B10H10)]Ru(dppm) (1c, dppm = bis(diphenylphosphino)methane), [η5:σ-Me2C(C5H4)(C2B10H10)]Ru(dppf) (1d, dppf = 1,1‘-bis(diphenylphosphino)ferrocene), and [η5:σ-Me2C(C5H4)(C2B10H10)]Ru(dppc) (1e, dppc = 1,2-(Ph2P)2-1,2-C2B10H10). 1a also reacted with 2,2‘-bipyridine (bipy) to offer [η5:σ-Me2C(C5H4)(C2B10H10)]Ru(bipy) (1f). However, 1a did not react

  用1个当量的合成将[RuCl碳桥连的环戊二烯基配位体碳硼烷的二锂盐的反应2（COD）] X的THF，得到有机钌（II）配合物[ η 5：σ -Me 2 C（ç 5 ħ 4）（ c ^ 2乙10 ħ 10）]钌（COD）（1A），[ η 5：σ -Me 2 C（ç 9 ħ 6）（C 2乙10 ħ 10）]钌（COD）（图2a）和[ η 5：分别为σ- H 2 C（C 13 H 8）（C 2 B 10 H 10）] Ru（COD）（3a）。的治疗1A与THF中的二齿的叔膦，得到相应的COD位移配合物[ η 5：σ -Me 2 C（ç 5 ħ 4）（C 2乙10 ħ 10）]钌（DPPE）（1B，DPPE = 1， 1,2-双（二苯基膦基）乙烷），[ η 5：σ -Me 2 C（C ^ 5 ħ4）（C 2乙10 ħ 10）]钌（DPPM）（1C，DPPM =双（二苯基膦基）甲烷），[ η 5：σ
• Deprotonation of ions pairs in aqueous solvent. Competing bimolecular and solvolytic elimination reactions
  作者：Alf Thibblin

  DOI：10.1021/ja00241a026

  日期：1987.4

  formation of a common contact ion pair (with a secondary isotope effect of 2.2) which either undergoes nucleophilic attack by water (isotope effect 1.0) or is deprotonated by water (isotope effect 2.8) ormore » other general base (including chloride and bromide anions). Direct elimination from the ion pairs is indicated by the observation that the fraction of elimination increases with rising basicity

  9-(2-氯-2-丙基)芴 (h-1-Cl) 或 9-(2-溴-2-丙基) 芴 (h-1-Br) 在 25 ℃ 的 25 vol% 乙腈水溶液中的溶剂分解生成 9-(2-丙烯基)芴 (h-4)、9-(2-羟基-2-丙基)芴 (h-2) 和痕量 9-异亚丙基芴 (h-3)。相应的乙酸盐 9-(2-乙酰氧基-2-丙基)芴 (h-1-OAc) 产生相同的产物，但 3 和 4 的数量相当。碱以及氯离子或溴离子的存在增加了消除分数产品但不增加 k12 + k14。用取代的乙酸根阴离子使碳阳离子中间体去质子化的布朗斯台德参数很小，约为 = 0.05。氘化类似物 9-(1,1,1,3,3,3,-SH6)-9-(2-氯-2-丙基)芴 (d6-1-Cl) 的反应比 h-1-Cl 慢。因此，在没有碱的情况下测量整体动力学同位素效应为 (k12/sup H/ + k13/sup H/ + k14/sup H/)/(k12/sup
• Diradical reaction mechanisms in [3 + 2]-cycloadditions of hetaryl thioketones with alkyl- or trimethylsilyl-substituted diazomethanes
  作者：Grzegorz Mlostoń、Paulina Pipiak、Heinz Heimgartner

  DOI：10.3762/bjoc.12.71

  日期：——

  carried out at -75 degrees C occur mainly via the initially formed, relatively stable 1,3,4-thiadiazolines as products of the [3 + 2]-cycloaddition of the diazo dipole onto the C=S bond. The latter decompose only at higher temperature (ca. -40 degrees C) to generate thiocarbonyl S-isopropanide. In the absence of the starting thioketone, the corresponding thiiranes and/or ethene derivatives, formed from

  在可变温度下研究了二杂芳基和芳基/杂芳基硫酮与2-重氮丙烷，重氮乙烷和（三甲基甲硅烷基）重氮甲烷的反应。实验表明，在-75摄氏度下与2-重氮丙烷进行的反应主要是通过最初形成的相对稳定的1,3,4-噻二唑啉作为重氮偶极子[3 + 2]环加成到C上的产物而发生的。 = S键。后者仅在较高的温度下（约-40摄氏度）分解，生成硫代羰基S-异丙烷。在不存在起始硫酮的情况下，通过自发脱硫由它们形成的相应的噻喃和/或乙烯衍生物是主要产物。相反，与重氮乙烷的反应主要是通过最初形成的双自由基发生的，而双自由基在级联过程中产生空间拥挤的4,4,5,5-四杂芳基-1，3-二硫杂环戊烷为主要产品。最后，二杂芳基硫酮与（三甲基甲硅烷基）重氮甲烷的反应在-75摄氏度下平稳进行，从而导致相应的4,4,5,5-四杂芳基-1,3-二硫杂环戊烷作为唯一的[3 + 2]-环加合物通过一叠假定的基数。杂芳基环中S或Se原子的存在